Abstract

Surface X-ray diffraction has been used to analyze in situ the room-temperature adsorption behaviour and the structure of K and Cs on Cu(100) at submonolayer coverages. Adsorption of K takes place in fourfold hollow sites up to coverages of about 0.25 monolayers (ML), where 1 ML corresponds to 1.53 × 1015 atoms/cm2. At higher coverages the formation of a quasi-hexagonal incommensurate adlayer is observed. In contrast, for Cs adsorption we observe from the very beginning the formation of the quasi-hexagonal structure up to the completion of the adlayer at about 0.30 ML. For K adsorption in the hollow sites we determine an adsorption height, d = 2.25(15) Å, corresponding to an effective K radius of reff = 1.6(1) Å close to the ionic radius of 1.33 Å. We do not observe a change in the effective radius as a function of coverage. For the quasi-hexagonal Cs structure we find an (average) adsorption height d = 2.94 Å corresponding to an effective radius of reff = 2.18 and 1.93 Å, for the limiting ca hollow- and bridge-site adsorption, respectively. The analysis of the superlattice reflections corresponding to the quasi-hexagonal incommensurate structures indicated that the K adlayer is strongly modulated. The first Fourier component of the substrate-induced modulation was determined to u01 = 1.29(3) Å. In contrast, for Cs/Cu(001) static modulation is much less important (u01 0.2 Å). Variation of the Cs adlayer density by changing the substrate temperature allows continuous expansion and contraction of the adsorbate unit cell. No commensurate-incommensurate transition has been observed.